Process for the production of chlorinated propenes

a chlorinated propene and propene technology, applied in the field of chlorinated propene production processes, can solve the problems of prohibitively high cost, limited commercial availability of many chlorinated propenes, and prohibitively expensive to be economically produced, etc., to achieve enhanced process selectivity, low cost, and fewer steps

Inactive Publication Date: 2014-03-20
BLUE CUBE IP
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Benefits of technology

[0007]The present invention provides efficient processes for the production of chlorinated propenes. Advantageously, the processes make use of 1,2-dichloropropane, a by-product in the production of chlorohydrin, as a low cost starting material, alone or in combination with 1,2,3-trichloropropane. Selectivity of the process is enhanced over conventional chlorination processes by employing successive chlorination steps, using an ionic chlorination catalyst, and dehydrochlorination steps. Because 1,2-dich

Problems solved by technology

Unfortunately, many chlorinated propenes may have limited commercial availability, and/or may only be available at prohibitively high cost, due at least in part to the complicated, multi-step processes typically utilized in their manufacture.
This may be due at least in part to the fact that conventional processes

Method used

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  • Process for the production of chlorinated propenes
  • Process for the production of chlorinated propenes
  • Process for the production of chlorinated propenes

Examples

Experimental program
Comparison scheme
Effect test

example i

[0080]In this example, liquid SO2Cl2 and PDC (1,2-dichloropropane) are mixed in a 100 ml flask heated in a water bath to maintain temperature 55° C. to 60° C. A reflux column is placed to return unreacted sulfuryl chloride and PDC, that are stripped by SO2 and HCl byproducts, to the reaction flask.

[0081]Table 1 shows the product distribution, as determined by GC / MS, at various SO2Cl2 and / or AIBN initiator concentrations at near complete PDC conversions. As shown by both Table 1 and FIG. 1, this process, using high excess SO2Cl2 at 45% total conversion to pentachloropropane isomers, provides less than 8% molar selectivity to the less desirable pentachloropropane, 1,1,2,3,3-pentachloropropane (11233).

TABLE 1SO2Cl2 / PDC33556AIBN / PDC02123PDC98.5%100.0%100.0%100.0%100.0%conversionSelectivity112233.3%3.7%5.0%11.8%19.4%112332.0%2.0%2.4%5.2%7.4%111221.3%1.7%2.5%6.3%10.7%111232.3%2.6%1.7%4.1%5.8% 112213.2%17.8%19.4%21.2%23.9% 112315.6%15.6%14.8%10.8%8.9% 122310.1%11.8%12.3%12.9%9.7% 11123.6%3...

example ii

[0082]In this example, PDC (10 mL) is mixed in a 100 ml pressure reactor with 2,2′-azobis(2,4-dimethyl valeronitrile) (100 mg), dimethyl 2,2′-azobis(2-methylpropionate) (100 mg) or 1,1′-azobis(cyclohexane-1-carbonitrile) (100 mg) in carbon tetrachloride solvent (37.2 mL). The reactor is heated using a heating mantle to a temperature of ˜70° C. A flow of gaseous Cl2 in N2 (30% v / v at STP) is passed through the mixture at a rate of about 100 sccm for the rest of the synthesis. A reactor pressure of ˜130 psig is maintained during the experiment. 1H NMR spectroscopy is used to determine the product composition.

[0083]Table 2 shows the chlorinated product distribution after about 200 and 300 minutes of chlorine passing through solution. As also shown in Table 2 or FIG. 1, less than 8% molar selectivity to the less desirable byproduct 1,1,2,3,3-pentachloropropane (11233) is observed at all conversions.

TABLE 22,2′-azobis(2,4-dimethyl 2,2′-1,1′-dimethylazobis(2-azobis(cyclohexane-valeronitri...

example iii

[0084]In this example, a 100 ml pressure reactor is charged with carbon tetrachloride (45 mL) and gaseous Cl2 in N2 (30% v / v at STP) is passed through the mixture while the pressure is held at about 150 psig until saturation is reached. The reactor is heated using a heating mantle to a temperature of ˜70° C. and while the pressure is maintained at about 150 psig. Then, a solution containing PDC (10 mL) and free radical initiator dimethyl 2,2′-azobis(2-methylpropionate) (100 mg) is added. 1H NMR spectroscopy is used to determine the product composition.

[0085]Table 3 shows the chlorinated C3 product distribution at various PDC conversions. As also shown in FIG. 1, less than 8% molar selectivity to the less desirable byproduct 1,1,2,3,3-pentachloropropane (11233) is observed at all conversions.

TABLE 3Sample 1Sample 2Time1732PDC98.999.6ConversionSelectivity112232.6%3.7%112331.1%1.6%111222.2%3.3%111230.7%1.0% 112220.1%23.0% 112311.5%12.1% 122310.9%12.3% 11123.5%3.6% 1128.5%6.2% 12329.9%2...

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Abstract

Processes for the production of chlorinated propenes are provided. The present processes make use of 1,2-dichloropropane, a by-product in the production of chlorohydrin, as a low cost starting material, alone or in combination with 1,2,3-trichloropropane. The present processes can also generate anhydrous HCl as a byproduct that can be removed from the process and used as a feedstock for other processes, providing further time and cost savings. Finally, the processes are advantageously conducted in the liquid phase, thereby presenting additional savings as compared to conventional, gas phase processes.

Description

FIELD[0001]The present invention relates to processes for the production of chlorinated propenes.BACKGROUND[0002]Hydrofluorocarbon (HFC) products are widely utilized in many applications, including refrigeration, air conditioning, foam expansion, and as propellants for aerosol products including medical aerosol devices. Although HFC's have proven to be more climate friendly than the chlorofluorocarbon and hydrochlorofluorocarbon products that they replaced, it has now been discovered that they exhibit an appreciable global warming potential (GWP).[0003]The search for more acceptable alternatives to current fluorocarbon products has led to the emergence of hydrofluoroolefin (HFO) products. Relative to their predecessors, HFOs are expected to exert less impact on the atmosphere in the form of a lesser, or no, detrimental impact on the ozone layer and their much lower GWP as compared to HFC's. Advantageously, HFO's also exhibit low flammability and low toxicity.[0004]As the environment...

Claims

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Application Information

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IPC IPC(8): C07C17/25
CPCC07C17/25C07C17/10C07C19/01C07C21/04
Inventor TIRTOWIDJOJO, MAX M.KRUPER, JR., WILLIAM J.FISH, BARRY B.LAITAR, DAVID S.
Owner BLUE CUBE IP
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